EP0193269A2 - Silica coating - Google Patents

Silica coating Download PDF

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Publication number
EP0193269A2
EP0193269A2 EP86300424A EP86300424A EP0193269A2 EP 0193269 A2 EP0193269 A2 EP 0193269A2 EP 86300424 A EP86300424 A EP 86300424A EP 86300424 A EP86300424 A EP 86300424A EP 0193269 A2 EP0193269 A2 EP 0193269A2
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Prior art keywords
coating
substrate
coated article
silica particles
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German (de)
French (fr)
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EP0193269B2 (en
EP0193269A3 (en
EP0193269B1 (en
Inventor
Roger W. C/O Minnesota Mining And Lange
Harold G. C/O Minnesota Mining And Sowman
Soon Kun C/O Minnesota Mining And Kang
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3M Co
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3M Co
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    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS, OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made
    • G02B1/10Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11Anti-reflection coatings
    • G02B1/113Anti-reflection coatings using inorganic layer materials only
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23Oxides
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00Coatings on glass
    • C03C2217/20Materials for coating a single layer on glass
    • C03C2217/21Oxides
    • C03C2217/213SiO2
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00Methods for coating glass
    • C03C2218/10Deposition methods
    • C03C2218/11Deposition methods from solutions or suspensions
    • C03C2218/113Deposition methods from solutions or suspensions by sol-gel processes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/256Heavy metal or aluminum or compound thereof
    • Y10T428/257Iron oxide or aluminum oxide
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/259Silicic material
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/26Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991Coated
    • Y10T428/2993Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31652Of asbestos
    • Y10T428/31663As siloxane, silicone or silane
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31652Of asbestos
    • Y10T428/31667Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31786Of polyester [e.g., alkyd, etc.]

Abstract

coated article having a substrate coated with a layer of silica particles is provided. The coating is substantially uniform in thickness, adheres aggressively to the substrate, and provides excellent antireflection properties to the substrate.

Description

    Background of the Invention Field of the Invention
  • The present invention relates to silica coatings, articles, such as optical devices, bearing silica coatings thereon, and to processes for preparing such articles.
  • Background Information
  • Improvement in the transmittance of light through optical devices such as windows, solar collector cover plates, lenses and prisms has long been sought so as to increase their usefulness. Optical devices having surfaces coated with antireflecting layers, typically having an optical thickness of one quarter of a wavelength, are known. Also known are optical devices in which surface reflections are reduced by altering the surface to provide a gradient index of refraction between that of the medium traversed by the incident light, such as air and that of the body of the optical device.
  • One method for providing such an altered surface is disclosed in Great Britain Patent No. 29,561. It involves tarnishing glass surfaces in aqueous solutions of sulphuretted hydrogen in order to reduce the reflection of light therefrom. Such a method is not useful for producing an antireflection surface on polymeric substrates.
  • Another method for providing such an altered surface is disclosed in Nicoll (U.S. Patent No. 2,445,238). This patent discloses a method for reducing reflection from glass surfaces in which the glass is heated in a vapor of hydrofluoric acid to form a skeletonized surface. Such skeletonized surfaces are difficult to reproduce and maintain.
  • Moulton (U.S. Patent No. 2,432,484) discloses a technique for forming a non-gelling, nonuniformly dispersed layer of anhydrous colloidal particles on the surface of articles. The particles form a random arrangement of peaks on the article surface to provide antireflection characteristics.
  • Moulton (U.S. Patent Nos. 2,536,764 and 2,601,123) discloses a transparent binder coating prepared using a dilute solution of tetraethylorthosilicate in organic solvent to render the colloidal particulate layer taught in the '484 patent resistant to wiping and handling, as such layers are inherently readily susceptable to injury.
  • Geffcken et al. (U.S. Patent No. 2,366,516) disclose an antireflection layer formed by applying an aqueous dispersion of a gel-like low-hydrated oxide, such as silicon dioxide, to an object and heating the coated object to a temperature of 2500c to form a hardened layer. Such a layer cannot be applied to most polymer substrates due to degradation of the substrate by heating to 2500C.
  • Baker et al. (U.S. Patent No. 3,301,701) disclose rendering a glass base antireflective by coating with a finely divided silica substantially free of silica gel. Such a coating would be expected to be brittle, weak, and powdery.
  • Land et al. (U.S. Patent No. 3,833,368) disclose antireflection coatings for photographic products which are an eighth-wave layer of a fluorinated polymer applied over an eighth-wave layer of silica, the silica layer having been formed from an aqueous colloidal silica sol.
  • Swerdlow (U.S. Patent No. 4,409,285) discloses an antireflection coating for optical surfaces, the coating formed from silica and/or alumina particles in a polymeric binder with particles protruding from the surface of the binder. 20 to 98 weight percent of the particles have a size in the range of 7 to 50 nanometers (nm) and 5 to 65 weight percent of the particles have a size in the range of 75 to 150 nm.
  • Yoldas (U.S. Patent Nos. 4,271,210 and 4,346,131) and McCollister et al. (U.S. Patent No. 4,273,826) disclose anti-reflection coatings produced by coating a substrate with a metallo-organic compound, e.g. alkoxide, and heating the coated substrate at temperatures which decompose the organic components of the coating leaving a metal oxide layer on the substrate. The temperatures necessary to decompose the organic components would also decompose polymeric substrates.
  • Dorer et al. (U.S. Patent No. 4,190,321) disclose an antireflective coating of a metal oxide in the form of discrete leaflets of varying heights and shapes. This coating is susceptible to damage during handling due to the fragility of the leaflet structure.
  • Cathro et al, (Silica Low-Reflection Coatings for Collector Covers, by a Dip-Coating Process, SOLAR ENERGY, Vol. 32, No. 5, 1984, pp. 573-579) disclose low-reflection silica coatings prepared from ethanol-based silica sols which are aged at pH 7. Aging causes an increase in optical density and viscosity due to the agglomeration of silica particles prior to coating. Although good adhesion of the coating to glass is said to be obtained by heating at elevated temperatures, adhesion to polymeric substrates is poor, i.e., the coating can be wiped from the surface of the substrate by rubbing with a tissue.
  • Summary of the Invention
  • The present invention is directed to a coated article comprising a substrate, particularly a polymeric substrate, having a silica coating thereon. The coating comprises a continuous, gelled network of silica particles which preferably have an average primary particle size of less than about 200A, more preferably less than about 70 A when antireflection properties are sought. The coating is substantially uniform in thickness and is substantially permanently adhered to the substrate, i.e. has a 180° peelback value of at least about 150 g/cm, preferably at least about 500 g/cm.
  • The present invention is also directed to a process for applying coatings to substrates comprising coating a substrate with a solution containing about 0.2 to 15 weight percent colloidal silica particles, the particles preferably having an average primary particle size of less than about 200 A, and drying the coating at a temperature less than that which degrades the substrate.
  • The coating adheres very well to a variety of substrates, particularly polymeric substrates, and can provide such substrates with excellent average reduction in specular reflectance, e.g., at least two percent. When the substrate is transparent, the coating can provide an average increase in transmission therethrough of normal incident light in the wavelength range of 400 to 800 nm over the transmission through an uncoated substrate of the same material. The increase in transmission is preferably at least two percent and up to as much as ten percent or more. The coating can also provide antistatic properties and reduced surface resistivity to substrates, such as polymeric film and sheet materials, subject to static build-up. The coating also preferably provides abrasion resistance and slip properties to polymeric materials, such as film and sheet materials, thereby improving their handleability.
  • Brief Description of the Drawings
    • Fig. 1 is a transmission electron micrograph of a cross section of an article of the invention;
    • Fig. 2 is a plot of a curve 2 of the percentage of light reflected from an uncoated polyethylene terephthalate film substrate and of a curve 3 of a coated polyethylene terephthalate film substrate according to the invention; and
    • Fig. 3 is a plot of a curve 4 of the percentage of light transmitted through an uncoated polyethylene terephthalate film substrate and of a curve 5 of a coated polyethylene terephthalate film substrate according to the invention.
    Detailed Description of the Invention
  • The article of the invention is a substrate bearing a continuous gelled network of silica particles. The particles preferably have an average primary particle size of less than about 200 A. As used herein, the term "continuous" refers to covering the surface of the substrate with virtually no discontinuities or gaps in the areas where the gelled network is applied. The term "gelled network" refers to an aggregation of colloidal particles linked together to form a porous three-dimensional network. The term "porous" refers to the presence of voids between the silica particles. The term "primary particle size" refers to the average size of unagglomerated single particles of silica.
  • The articles of the invention comprise a substrate which may be of virtually any construction, transparent to opaque, polymeric, glass, ceramic, or metal, having a flat, curved, or complex shape and have formed thereon a continuous gelled network of silica particles. When the coating is applied to transparent substrates to achieve increased light transmissivity, the coated article preferably exhibits a total average increase in transmissivity of normal incident light of at least two percent and up to as much as ten percent or more, depending on the substrate coated, over a range of wavelengths extending at least between 400 to 800 nm. An increase in transmissivity can also be seen at wavelengths into the infrared portion of the spectrum.
  • The polymeric substrates may comprise polymeric sheet, film, or molded material such as polyester, polyimide, polystyrene, polymethylmethacrylate, polycarbonate, polysulfone, polyacrylate, and cellulose acetate butyrate.
  • Figure 1, a transmission electron micrograph of a coating 1 useful in the invention at a magnification of 300,OOOX, shows that the coating is continuous, i.e., covers the surface of the substrate with virtually no discontinuities or gaps, and provides a substantially smooth surface which has only minor surface imperfections. Fig. 1 further shows that the coating 1 . is substantially uniform in thickness.
  • The coating useful in the invention is substantially permanently adhered to substrates to which it is applied, i.e., it can provide a 180° peelback value of at least about 150 g/cm when tested according to a modification of ASTM Test Method D3330. Generally, adhesion values of 500 g/cm can be achieved with failure at the adhesive layer and no coating removal from the substrate. In the modified test method, a 1.9 cm wide strip of Scotch Brand Magic transparent tape, available from 3M Company, is adhered to the test sample by rolling a 2 kg roller back and forth twice across the tape. The tape is then peeled from the test sample at 180° at a rate of 2 cm/min.
  • The excellent adhesion of the coating to the substrate and the adhesive of the test tape also demonstrates the utility of the coating as a primer for adhering adhesives to substrates, such as polymeric substrates, e.g, polyester films.
  • The gelled network provides a porous coating having voids between the silica particles. If the open porosity is too small, the properties of the coating, such as adhesion and antireflectance may be reduced. If the open porosity is too large, the coating is weakened and may have reduced adhesion to the substrate. Generally, the colloidal solution from which the gelled network is obtained is capable of providing an open porosity of about 25 to 70 percent, preferably about 30 to 60 percent when dried. The open porosity is determined by drying a sufficient amount of the colloidal solution to provide a dried product sample of about 50 to 100 mg and analyzing the sample using a "Quantasorb" surface area analyzer available from Quantachrome Corp., Syosett, NY.
  • The voids of the porous coating provide a multiplicity of subwavelength interstices where the index of refraction abruptly changes from that of air to that of the coating material. These subwavelength interstices which are present throughout the coating layer, provide a coating which may have a calculated index of refraction of from about 1.15 to 1.40, preferably 1.20 to 1.30 depending on the porosity of the coating. When the porosity of the coating is high, e.g., about 70 percent, lower values for the index of refraction are obtained. When the porosity of the coating is low, e.g., 25 percent, higher values for the index of refraction are obtained. The index of refraction of the coating is dependent on the relative volume ratios of the particles and the interstices and the index of refraction of the silica, i.e., 1.47. For purposes of this invention, the index of refraction (RI) is calculated using the formula:
    Figure imgb0001
    where Pa is the value of the open porosity.
  • The average primary particle size of the colloidal silica particles is preferably less than about 200 A to achieve good adhesion of the coating to the substrate. The average primary particle size of the colloidal silica particles is more preferably less than about 70 A when antireflection properties are sought. When the average particle size becomes too large, the resulting dried coating surface is less efficient as an antireflection coating.
  • The dried coating is preferably from about 20 to 500 nm thick. Such coatings provide good adhesion and antistatic properties. When the coating thickness is too great, the coating has reduced adhesion and flexibility and may flake off or form powder under mechanical stress. When antireflection properties are sought, the dried coating thickness is preferably about 70 to 250 nm, more preferably 100 to 200 nm.
  • Articles such as transparent sheet or film materials may be coated on a single side or on both sides to increase transmissivity, the greatest increase being achieved by coating both sides.
  • The process of the invention comprises coating a substrate with a solution containing about 0.2 to 15 weight percent colloidal silica particles having an average primary particle size less than about 200 A, preferably less than about 70 A, and drying the coating at a temperature less than about 200°C, preferably in the range of 80 to 120°C.
  • Coating may be carried out by standard coating techniques such as bar coating, roll coating, curtain coating, rotogravure coating, spraying and dipping. The substrate may be treated prior to coating to obtain a uniform coating. Various known treatment techniques include corona discharge, flame treatment, and electron beam. Generally, no pretreatment is required.
  • The colloidal silica solution, e.g., a hydrosol or organosol, is applied to the substrate of the article to be coated and dried at a moderately low temperature, generally less than about 200°C, preferably 80-1200C to remove water or organic diluents. The coating may also be dried at room temperature, provided the drying time is sufficient to permit the coating to dry completely. The drying temperature should be less than that at which the substrate degrades. The resulting hygroscopic coating is capable of absorbing and/or rehydrating water in an amount of up to about 15 to 20 weight percent, depending on ambient temperature and humidity conditions.
  • The colloidal silica solution, finely divided solid silica particles of ultramicroscopic size in a liquid, utilized in the present invention, may be acid stabilized, sodium stabilized, or ammonia stabilized. It is generally helpful to acidify sodium stabilized silica sols to a pH of about 3.5 to 4.0, e.g., with glacial acetic acid, to prevent particle agglomeration prior to preparation of the coating solution when alcohol is used as a diluent. Examples of commercially available colloidal silicas useful in the invention include Nalco 2326 and Nalco 1034A, available from Nalco Chemical Co., and Ludox LS, available from E. I. duPont de Nemours Co., Inc.
  • The colloidal coating solution should contain about 0.2 to 15 weight percent, preferably about 0.5 to 6 weight percent, colloidal silica particles. At particle concentrations above 15 weight percent, the resulting coating may have reduced uniformity and exhibit reduced adhesion to the substrate surface. Difficulties in obtaining a sufficiently thin coating to achieve increased light transmissivity and reduced reflection may also be encountered at concentrations above 15 weight percent. At concentrations below 0.2 weight percent, process inefficiencies result due to the large amount of solvent which must be removed and antireflection properties may be reduced.
  • The thickness of the applied wet coating solution is dependent on the concentration of silica particles in the coating solution and the desired thickness of the dried coating. The thickness of the wet coating solution is preferably such that the resulting dried coating thickness is from about 20 to 500 nm thick.
  • The coating solution may also optionally contain a surfactant to improve wettability of the solution on the substrate, but inclusion of an excessive amount of surfactant may reduce the adhesion properties of the coating. Examples of suitable surfactants include Tergitol TMN-6 (Union Carbide Corp.) and Triton X-100 (Rohm and Haas Co.). Generally, the surfactant can be used in amounts of up to about 0.5 weight percent of the solution.
  • The coating ingredients may optionally contain a polymeric binder. Useful polymeric binders include polyvinyl alcohol, polyvinyl acetate, polyesters, polyamides, polyvinyl pyrrolidone, copolyesters, copolymers of acrylic acid and/or methacrylic acid, and copolymers of styrene. The coating solution can contain up to about 50 weight percent of the polymeric binder based on the weight of the silica particles. Useful amounts of polymeric binder are generally in the range of 0.5 to 10.0 weight percent.
  • Addition of various adjuvants, such as slip agents and processing oils, to the substrate material may reduce the adhesion of the coating to the substrate.
  • The following specific, but non-limiting, examples will serve to illustrate the invention. In these examples, all percentages and parts are by weight unless otherwise indicated.
  • Example 1
  • Six grams of Nalco 2326 (ammonia stabilized colloidal silica; 14.5% colloidal silica as SiO 2; particle size 50A; available from Nalco Chemical Company) was added to 100 g ethanol to provide a very clear coating solution. A 0.1 mm biaxially oriented polyethylene terephthalate film containing an ultraviolet absorber was dipped in the coating solution, air dryed, and dried at 1000C for two minutes. The resulting coating was porous, continuous, and similar to the coating shown in Fig. 1 in appearance. The coating thickness was about 120 nm.
  • The coating adhered aggressively to the substrate. A 3/4 inch wide strip of Scotch Brand Magic transparent tape was applied to coated and uncoated film samples by hand pressure. A force of about 180 g/cm tape width was required to remove the tape from the uncoated sample, while a force of about 530 g/cm tape width was required to remove the tape from the coated sample, demonstrating a remarkable increase in the adhesion of the tape. The adhesive of the tape did not remove the coating from the coated film, but exhibited adhesive split of the adhesive layer leaving adhesive residue on the coating further demonstrating the strong bond of the adhesive to the coated film. No adhesive split was observed when the tape was removed from the uncoated sample.
  • The antireflection and transmission properties of the film were measured using an IBM UV-VIS 9432 Spectrophotometer at wavelengths of from 350 to 800 nm. An uncoated sample of the film was also measured for comparative purposes. The results of these tests are shown in Figs. 2 and 3. As can be seen from Fig. 2, the reflectance of the uncoated sample, curve 2, was about 12% at 600 nm, while the reflectance of the coated sample, curve 3, was about 2% at 600 nm. As can be seen from Fig. 3, the light transmission of the uncoated film, curve 4, was about 88% at 600 nm, while the light transmission of the coated sample, curve 5, was about 98% at 600 nm. This demonstrates the excellent reduction of reflectance and increase in transmission of light provided by the coating.
  • Example 2
  • A coating solution was prepared by diluting colloidal silica (Nalco 2326) with ethanol to a concentration of 2.5% solids and adding 0.01% Tergitol TMN-6. The solution was coated on 0.1 mm thick polyethylene terephthalate film using a rotogravure coating roll. The coated film was dried at 93°C for three minutes. The resulting coating was porous, continuous, and about 100 nm thick. The coating was substantially similar to the coating shown in Fig. 1. The dried coating was observed to have good antireflection-properties.
  • Samples of the coated film as well as samples of uncoated film were tested for adhesion using the modified ASTM Test Method D3330 described hereinabove. The uncoated film had an adhesion value of 189 g/cm tape width with no adhesive split from the tape. The coated sample had an adhesion value of 559 g/cm tape width. The tape did not remove the coating from the film, but exhibited adhesive split of the adhesive layer, again demonstrating the excellent adhesion of the coating to the substrate and the excellent adhesion of the adhesive to the coating.
  • Examples 3-15
  • Various transparent polymeric sheet materials, as identified in Table 1, were coated by dipping the materials in a coating solution containing 1.5% colloidal silica (Nalco 2326) or by wiping the solution on each side of the sheet material with a tissue-wrapped glass rod and drying the coated sample.
    Figure imgb0002
  • The following coating solutions were used to coat the various sheet materials:
  • Solution I
  • Figure imgb0003
  • Solution II
  • Figure imgb0004
  • For each example, the substrate material, coating method, coating solution, and drying temperature, together with the resulting light transmission determined using an IBM UV-VIS 9432 Spectrophotometer at wavelengths of from 400 to 800 nm, are set forth in Table 2. Light transmission data for uncoated materials are also set forth in Table 2 for comparative purposes.
  • Figure imgb0005
  • As can be seen from the data in Table 2, the coatings provide an excellent increase in light transmission for each of the materials which were coated. Each coated sample exhibited at least two percent average increase in light transmission. The greatest increase in transmission was achieved on the CR-39 polycarbonate with the average percent increase in transmission for Example 7 being 6.8 percent.
  • Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the scope and spirit of this invention.

Claims (16)

1. A coated article comprising a substrate having a coating of a continuous, gelled network of silica particles which coating is substantially uniform in thickness and is substantially permanently adhered to said substrate.
2. The coated article of claim 1 wherein said silica particles have a primary particle size of less than about 200 A.
3. The coated article of claim 1 wherein said coating provides a 1800 peelback value of at least about 150 g/cm.
4. The coated article of claim 1 wherein said coating is about 20 to 500 nm thick.
5. The coated article of claim 1 wherein said coating is prepared from a colloidal solution capable of providing a dried product having an open porosity of between about 25 and 70 percent.
6. The coated article of claim 1 wherein said coating contains up to about 20 weight percent water.
7. The coated article of claim 1 wherein said substrate is transparent.
8. The coated article of claim 7 wherein the transmission therethrough of normal incident light in the wavelength range of 400 to 800 nm is increased over the transmission through an uncoated substrate of the same composition.
9. The coated article of claim 8 wherein said average transmission is increased at least 2 percent.
10. The coated article of claim 8 wherein said coating is from about 70 to 250 nm thick.
11. The coated article of claim 8 wherein said coating has an index of refraction of between about 1.15 and 1.40.
12. The coated article of claim 1 or 7 wherein said substrate is polymeric.
13. The process for forming coated article of claim 1 comprising coating said substrate with a solution containing colloidal silica particles, and drying said coating at a temperature less than that which degrades said substrate to form a substantially continuous, gelled network of silica particles which is substantially uniform in thickness and is substantially permanently adhered to said substrate.
14. The process of claim 13 wherein said particles have an average primary particle size of less than about 200 A.
15. The process of claim 13 wherein the coating is dried at a temperature of less than 200°C.
16. The process of claim 13 wherein the coating is dried at a temperature in the range of 800C to 120°C.
EP19860300424 1985-01-25 1986-01-22 Silica coating Expired - Lifetime EP0193269B2 (en)

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US69494585A true 1985-01-25 1985-01-25
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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4755425A (en) * 1987-03-09 1988-07-05 Minnesota Mining And Manufacturing Company Retroreflective sheet coated with silica layer
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GB2220502A (en) * 1988-07-09 1990-01-10 Exitech Ltd Excimer laser beam homogenizer system
US5073404A (en) * 1987-03-09 1991-12-17 Minnesota Mining And Manufacturing Company Silica coating composition for reflective sheeting
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Families Citing this family (76)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5204219A (en) * 1987-07-30 1993-04-20 Minnesota Mining And Manufacturing Company Photographic element with novel subbing layer
DE3827631A1 (en) * 1988-08-16 1990-02-22 Hoechst Ag Self-supporting flaechengebilde with at least one structured surface
US5612128A (en) * 1988-09-09 1997-03-18 Hitachi, Ltd. Ultra fine particles having uneven surfaces and treatment plate using same
US5328768A (en) * 1990-04-03 1994-07-12 Ppg Industries, Inc. Durable water repellant glass surface
US5639546A (en) * 1991-09-03 1997-06-17 Minnesota Mining And Manufacturing Company Coated article having improved adhesion to organic coatings
US5747171A (en) * 1991-09-20 1998-05-05 Eka Chemicals Ab Method of protecting a surface
US5726782A (en) * 1991-10-09 1998-03-10 Nippondenso Co., Ltd. Hologram and method of fabricating
DE69218785D1 (en) * 1991-10-11 1997-05-07 Minnesota Mining & Mfg Thin image-transfer layer
US5278243A (en) * 1992-01-14 1994-01-11 Soane Technologies, Inc. High impact resistant macromolecular networks
US5873931A (en) * 1992-10-06 1999-02-23 Minnesota Mining And Manufacturing Company Coating composition having anti-reflective and anti-fogging properties
US5585186A (en) * 1994-12-12 1996-12-17 Minnesota Mining And Manufacturing Company Coating composition having anti-reflective, and anti-fogging properties
US6040053A (en) * 1996-07-19 2000-03-21 Minnesota Mining And Manufacturing Company Coating composition having anti-reflective and anti-fogging properties
US5615767A (en) * 1995-04-11 1997-04-01 Minnesota Mining And Manufacturing Company Method and packaging for surgical masks
US5847795A (en) * 1995-07-27 1998-12-08 Canon Kabushiki Kaisha Liquid crystal display apparatus and anti-reflection film applicable thereto
US5753373A (en) * 1995-12-21 1998-05-19 Minnesota Mining And Manufacturing Company Coating composition having anti-reflective and anti-fogging properties
EP0790138B1 (en) 1996-02-15 1999-10-20 Minnesota Mining And Manufacturing Company Laser-induced thermal transfer imaging process
US5846650A (en) * 1996-05-10 1998-12-08 Minnesota Mining And Manufacturing Company Anti-reflective, abrasion resistant, anti-fogging coated articles and methods
US5948481A (en) * 1996-11-12 1999-09-07 Yazaki Corporation Process for making a optical transparency having a diffuse antireflection coating
JPH10259038A (en) 1997-01-24 1998-09-29 Samsung Corning Co Ltd Durable water-repelling glass and its production
US5993898A (en) * 1997-05-19 1999-11-30 Nikon Corporation Fabrication method and structure for multilayer optical anti-reflection coating, and optical component and optical system using multilayer optical anti-reflection coating
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US6623791B2 (en) 1999-07-30 2003-09-23 Ppg Industries Ohio, Inc. Coating compositions having improved adhesion, coated substrates and methods related thereto
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US6635341B1 (en) * 2000-07-31 2003-10-21 Ppg Industries Ohio, Inc. Coating compositions comprising silyl blocked components, coating, coated substrates and methods related thereto
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2536764A (en) * 1947-04-05 1951-01-02 American Optical Corp Method of forming a reflection reducing coating
US2601123A (en) * 1947-04-05 1952-06-17 American Optical Corp Composition for reducing the reflection of light
US3707751A (en) * 1967-05-05 1973-01-02 Mbt Corp Dampening roller having hydrophilic surface coating
US3986997A (en) * 1974-06-25 1976-10-19 Dow Corning Corporation Pigment-free coating compositions
US4271210A (en) * 1979-10-25 1981-06-02 Westinghouse Electric Corp. Method of forming transmissive, porous metal oxide optical layer of a vitreous substrate
JPS58126502A (en) * 1982-01-25 1983-07-28 Nippon Sheet Glass Co Ltd Antireflection plastic optical parts
US4409285A (en) * 1980-11-10 1983-10-11 Imperial Chemical Industries Plc Surface-modifying coating compositions
EP0130801A1 (en) * 1983-06-29 1985-01-09 Westinghouse Electric Corporation Improvements in or relating to antireflective silica coatings

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB190429561A (en) * 1904-12-31 1905-11-23 Harold Dennis Taylor A Method of Increasing the Brilliancy of the Images Formed by Lenses.
CH219890A (en) * 1939-05-27 1942-03-15 Jenaer Glaswerk Schott & Gen A process for producing one or more superimposed, thin, resistant coatings on solid objects.
US2432484A (en) * 1943-03-12 1947-12-09 American Optical Corp Reflection reducing coating having a gradually increasing index of refraction
US2445238A (en) * 1946-10-08 1948-07-13 Rca Corp Production of skeletonized low reflectance glass surface with fluosilicic acid vapor
BE540601A (en) * 1950-12-06
GB1061784A (en) * 1962-08-22 1967-03-15 Ozalid Co Ltd Improvements in or relating to the treatment of polyester materials
DE1914057A1 (en) * 1968-03-25 1969-10-23 Bexford Ltd Copolymers of vinyl halo esters and methods for their preparation
US3301701A (en) * 1965-06-25 1967-01-31 Philadelphia Quartz Co Nonreflective glass coatings
US3485658A (en) * 1965-07-22 1969-12-23 Du Pont Plural monolayer coated article and process of making
US3380876A (en) * 1967-06-20 1968-04-30 Du Pont Bonding thermoplastic materials to substrates with colloidal silica
US3706589A (en) * 1969-06-19 1972-12-19 Tadanori Fukuda Method for temporarily protecting the surfaces of an article
US3914469A (en) * 1972-08-09 1975-10-21 Richard Delano Method of controlling solar heat and light in green houses
US3833368A (en) * 1972-12-04 1974-09-03 Polaroid Corp Photographic products incorporating anti-reflection coatings
SE420596B (en) * 1975-03-25 1981-10-19 Osaka Packing Shaped body of amorphous silica, optionally containing calcium carbonates, seen to be Stella a shaped body of amorphous silica and particles of amorphous silica was tell up of a shaped body
US4190321A (en) * 1977-02-18 1980-02-26 Minnesota Mining And Manufacturing Company Microstructured transmission and reflectance modifying coating
US4177315A (en) * 1977-03-04 1979-12-04 E. I. Du Pont De Nemours And Company Coated Polymeric substrates
US4346131A (en) * 1979-08-10 1982-08-24 Westinghouse Electric Corp. Polymerized solutions for depositing optical oxide coatings
GB2064987B (en) * 1979-11-14 1983-11-30 Toray Industries Process for producing transparent shaped article having enhanced anti-reflective effect
US4273826A (en) * 1979-12-03 1981-06-16 Owens-Illinois, Inc. Process of making glass articles having antireflective coatings and product
JPS57147526A (en) * 1981-03-06 1982-09-11 Mitsubishi Petrochem Co Ltd Surface modification of synthetic resin formed article
EP0111385A1 (en) * 1982-11-26 1984-06-20 Dow Corning Corporation Antimony oxide-containing organosilicon resins
JPS59204669A (en) * 1983-05-06 1984-11-20 Asahi Glass Co Ltd Composition for abrasion-resistant coating film

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2536764A (en) * 1947-04-05 1951-01-02 American Optical Corp Method of forming a reflection reducing coating
US2601123A (en) * 1947-04-05 1952-06-17 American Optical Corp Composition for reducing the reflection of light
US3707751A (en) * 1967-05-05 1973-01-02 Mbt Corp Dampening roller having hydrophilic surface coating
US3986997A (en) * 1974-06-25 1976-10-19 Dow Corning Corporation Pigment-free coating compositions
US4271210A (en) * 1979-10-25 1981-06-02 Westinghouse Electric Corp. Method of forming transmissive, porous metal oxide optical layer of a vitreous substrate
US4409285A (en) * 1980-11-10 1983-10-11 Imperial Chemical Industries Plc Surface-modifying coating compositions
JPS58126502A (en) * 1982-01-25 1983-07-28 Nippon Sheet Glass Co Ltd Antireflection plastic optical parts
EP0130801A1 (en) * 1983-06-29 1985-01-09 Westinghouse Electric Corporation Improvements in or relating to antireflective silica coatings

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN, vol. 7, no. 238 (P-231)[1383], 22nd October 1983; & JP-A-58 126 502 (NIHON ITA GLASS K.K.) 28-07-1983 *

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4755425A (en) * 1987-03-09 1988-07-05 Minnesota Mining And Manufacturing Company Retroreflective sheet coated with silica layer
US5073404A (en) * 1987-03-09 1991-12-17 Minnesota Mining And Manufacturing Company Silica coating composition for reflective sheeting
EP0309276A2 (en) * 1987-09-24 1989-03-29 Minnesota Mining And Manufacturing Company Primer for surfaces containing inorganic oxide
EP0309276A3 (en) * 1987-09-24 1990-03-28 Minnesota Mining And Manufacturing Company Primer for surfaces containing inorganic oxide
GB2220502A (en) * 1988-07-09 1990-01-10 Exitech Ltd Excimer laser beam homogenizer system
FR2680583A1 (en) * 1991-08-22 1993-02-26 Commissariat Energie Atomique Material having antiglare, hydrophobic and abrasion-resistant properties and process for depositing an antiglare, hydrophobic and abrasion-resistant layer on a substrate
WO1993004386A1 (en) * 1991-08-22 1993-03-04 Commissariat A L'energie Atomique Material having antireflection, hydrophobic and abrasion resistance properties, and method of depositing an antireflection, hydrophobic, abrasion resistant coating on a substrate
FR2762097A1 (en) * 1997-04-10 1998-10-16 Corning Sa Optical article with anti=reflective coating
EP0973639A1 (en) * 1997-04-10 2000-01-26 Corning Incorporated Optical article with anti-reflecting coating, corresponding coating material and coating method
EP0973639A4 (en) * 1997-04-10 2000-07-19 Corning Inc Optical article with anti-reflecting coating, corresponding coating material and coating method
WO1999063958A1 (en) * 1998-06-05 1999-12-16 Crosfield Limited Particulate materials for use in dentifrice compositions
US6479036B1 (en) 1998-06-05 2002-11-12 Crosfield Limited Particulate materials for use in dentifrice compositions
EP1760497A3 (en) * 2005-09-02 2009-08-26 Hitachi, Ltd. Optical part and projection type display apparatus using same
US7616380B2 (en) 2005-09-02 2009-11-10 Hitachi, Ltd. Optical part and projection type display apparatus using same
DE102006023375A1 (en) * 2006-05-17 2007-11-22 Nano-X Gmbh coating material
WO2009012141A3 (en) * 2007-07-13 2009-05-28 Alcon Inc Off-axis anti-reflective intraocular lenses
WO2009012141A2 (en) * 2007-07-13 2009-01-22 Alcon, Inc. Off-axis anti-reflective intraocular lenses
US7998197B2 (en) 2007-07-13 2011-08-16 Novartis Ag Off-axis anti-reflective intraocular lenses
WO2009062871A1 (en) * 2007-11-12 2009-05-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Use of a coated, transparent substrate for influencing the human psyche
EP2236472A1 (en) * 2008-11-11 2010-10-06 Schott AG Method for applying a porous antireflection coating and glass with antireflection coating
US9465145B2 (en) 2010-10-20 2016-10-11 3M Innovative Properties Company Low refractive index diffuser element having interconnected voids
WO2012150410A1 (en) * 2011-05-05 2012-11-08 Saint-Gobain Glass France Transparent substrate clad with a stack of mineral layers one of which is porous and covered
FR2974800A1 (en) * 2011-05-05 2012-11-09 Saint Gobain Transparent substrate coated with a stack of layers including a porous mineral covered
EA028716B1 (en) * 2011-05-05 2017-12-29 Сэн-Гобэн Гласс Франс Transparent substrate clad with a stack of mineral layers one of which is porous and covered

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DE3687757T3 (en) 2004-06-17
ES8708063A1 (en) 1987-09-01
HK101194A (en) 1994-09-30
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SG105494G (en) 1994-10-28
EP0193269B2 (en) 2003-10-22
BR8600124A (en) 1986-09-23
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AU5189586A (en) 1986-07-31
ES550782A0 (en) 1987-09-01
JPS61173936A (en) 1986-08-05
EP0193269A3 (en) 1989-03-08
US4816333A (en) 1989-03-28
EP0193269B1 (en) 1993-02-17
US4816333B1 (en) 1999-11-02
CA1275208C (en) 1990-10-16
DE3687757T2 (en) 1993-07-08
AR241192A1 (en) 1992-01-31

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